Golf ball material and golf ball

ABSTRACT

A mixture having good thermal stability, flow and moldability and suitable as a golf ball-forming material is obtained when a resinous component including a base resin of an ionomer resin or resins and optionally a non-ionomer thermoplastic elastomer is blended with specific proportions of a fatty acid and/or fatty acid derivative and a basic inorganic metal compound capable of neutralizing acidic groups left unneutralized in the base resin and fatty acid. Using the same material, high-rebound golf balls can be effectively manufactured.

[0001] The present invention relates to golf ball materials which havegood thermal stability, flow characteristics and moldability, and whichare capable of providing high-performance golf balls endowed withoutstanding rebound energy. The invention relates also to golf ballsmade with such golf ball materials.

BACKGROUND OF THE INVENTION

[0002] Over the past few years, wide use has been made of ionomer resinsin golf ball cover materials, also referred to hereinafter as “coverstock”. Ionomer resins are ionic copolymers composed of an olefin suchas ethylene in combination with an unsaturated carboxylic acid such asacrylic acid, methacrylic acid or maleic acid, wherein the acidic groupsare partially neutralized with metal ions such as sodium, lithium, zincor magnesium ions. They have excellent characteristics such asdurability, resilience and scuff resistance.

[0003] Ionomer resins account for most of the cover stock resin incurrent use. A variety of improvements have been made thereon becausegolfers are always on the lookout for golf balls having a high reboundand excellent flight characteristics.

[0004] Related improvements taught by the prior art (see U.S. Pat. Nos.5,312,857, 5,306,760, and International Application WO 98/46671) includecover stock in which a large amount of metallic soap is added to theionomer resin to improve the cost and rebound characteristics of theionomer cover stock.

[0005] These cover stocks, however, fall far short of practical levels.During injection molding, the metallic soap in the cover stockdecomposes and vaporizes to generate a large amount of fatty acid gas,often causing molding defects. In addition, gas constituents settle onthe surface of the molded part to greatly lower the paintabilitythereof. Moreover, although such cover stock in which a large amount ofmetallic soap has been added to the ionomer resin does exhibit a reboundwhich is about the same as or better than that of metallic soap-freeionomer cover stock having the same degree of hardness, the improvementin rebound is not all that large. Indeed, depending on the type ofmetallic soap used, the moldability and rebound of cover stock may infact be severely compromised.

SUMMARY OF THE INVENTION

[0006] Therefore, one object of the invention is to provide golf ballmaterials which have good thermal stability, flow and moldability, andwhich are capable of providing golf balls of outstanding rebound.Another object of the invention is to provide golf balls made using suchgolf ball materials.

[0007] Quite unexpectedly, it has been found that a mixture having goodthermal stability, flow and moldability is obtained when 100 parts byweight of a resinous component in which a base resin having (a) anolefin-unsaturated carboxylic acid binary random copolymer and/or ametal ion-neutralized olefin-unsaturated carboxylic acid binary randomcopolymer blended with (b) an olefin-unsaturated carboxylicacid-unsaturated carboxylate ternary random copolymer and/or a metalion-neutralized olefin-unsaturated carboxylic acid-unsaturatedcarboxylate ternary random copolymer in a weight ratio of 100:0 to 25:75is blended with (e) a non-ionomer thermoplastic elastomer in a weightratio of 100:0 to 50:50, is blended with (c) 5 to 80 parts by weight ofa fatty acid and/or fatty acid derivative having a molecular weight of280 to 1,500 and (d) 0.1 to 10 parts by weight of a basic inorganicmetal compound capable of neutralizing acidic groups left unneutralizedin the base resin and component (c). The mixture is suitable forinjection molding and a molded part thereof exhibits improved reboundcharacteristics. The mixture is thus best suited as a golf ballmaterial.

[0008] The molded part of the above-described golf ball material canform any desired constituent component of a golf ball (which is selectedfrom among a one-piece golf ball, solid core, solid center, cover andother components). The golf ball thus constructed has very good reboundand improved initial velocity performance. The invention is predicatedon these findings.

[0009] According to the invention, there is provided a golf ballmaterial comprising a mixture which is composed of essential components:

[0010] 100 parts by weight of a resinous component consistingessentially of

[0011] a base resin having (a) an olefin-unsaturated carboxylic acidbinary random copolymer and/or a metal ion-neutralizedolefin-unsaturated carboxylic acid binary random copolymer, blended with(b) an olefin-unsaturated carboxylic acid-unsaturated carboxylateternary random copolymer and/or a metal ion-neutralizedolefin-unsaturated carboxylic acid-unsaturated carboxylate ternaryrandom copolymer, in a weight ratio of 100:0 to 25:75, and

[0012] (e) a non-ionomer thermoplastic elastomer, the base resin and theelastomer being blended in a weight ratio of 100:0 to 50:50;

[0013] (c) 5 to 80 parts by weight of a fatty acid and/or fatty acidderivative having a molecular weight of 280 to 1,500; and

[0014] (d) 0.1 to 10 parts by weight of a basic inorganic metal compoundcapable of neutralizing acidic groups left unneutralized in the baseresin and component (c).

[0015] Preferably, the mixture has a melt flow rate of 0.5 to 20 dg/min.Also preferably, at least 50 mol % of the acid groups in the mixture areneutralized with metal ions. The metal ions are preferably comprised ofat least one type of transition metal ion and at least one type ofalkali metal or alkaline earth metal ion. More preferably, thetransition metal ions and the alkali metal or alkaline earth metal ionsare in a molar ratio of 10:90 to 90:10.

[0016] In a preferred embodiment, the metal ion-neutralized randomcopolymer in the base resin includes a zinc ion-neutralized ionomerresin.

[0017] The total content of random copolymers and the total content ofmetal ion-neutralized random copolymers in the base resin are preferablyin a weight ratio of 0:100 to 60:40.

[0018] In a preferred embodiment, component (c) is selected from amongstearic acid, behenic acid, arachidic acid, lignoceric acid andderivatives thereof. Typically, component (d) is calcium hydroxide. Alsopreferably, component (e) is selected from among an olefin elastomer,styrene elastomer, polyester elastomer, urethane elastomer, andpolyamide elastomer.

[0019] In another aspect, the invention provides a golf ball comprisinga molded part of the golf ball material set forth above. Preferably, themolded part has a Shore D hardness of 50 to 75. Also contemplated hereinis a multi-piece solid golf ball comprising a core, a cover inner layerand a cover outer layer, wherein the cover inner layer is a molded partof the golf ball material set forth above.

DETAILED DESCRIPTION OF THE INVENTION

[0020] The golf ball material of the invention contains as an essentialcomponent a base resin having (a) an olefin-unsaturated carboxylic acidbinary random copolymer and/or a metal ion-neutralizedolefin-unsaturated carboxylic acid binary random copolymer blended with(b) an olefin-unsaturated carboxylic acid-unsaturated carboxylateternary random copolymer and/or a metal ion-neutralizedolefin-unsaturated carboxylic acid-unsaturated carboxylate ternaryrandom copolymer in a specific weight ratio.

[0021] In the base resin, the olefin, whether it belongs to component(a) or (b), generally has at least 2 carbon atoms, but not more than 8carbon atoms, and preferably not more than 6 carbon atoms. Illustrativeexamples include ethylene, propylene, butene, pentene, hexene, hepteneand octene. Ethylene is especially preferred.

[0022] Suitable examples of the unsaturated carboxylic acid includeacrylic acid, methacrylic acid, maleic acid and fumaric acid. Of these,acrylic acid and methacrylic acid are especially preferred.

[0023] The unsaturated carboxylate is preferably a lower alkyl ester ofthe foregoing unsaturated carboxylic acid. Illustrative examples includemethyl methacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and butylacrylate. Butyl acrylate (n-butyl acrylate, i-butyl acrylate) isespecially preferred.

[0024] The olefin-unsaturated carboxylic acid binary random copolymer(a) or olefin-unsaturated carboxylic acid-unsaturated carboxylateternary random copolymer (b), to be commonly referred to as “randomcopolymer” hereinafter, may be prepared by furnishing the aboveingredients and carrying out random copolymerization in a well-knownmanner.

[0025] It is recommended that the unsaturated carboxylic acid content(simply referred to as acid content) within the random copolymer beadjusted to an appropriate level. For the random copolymer (a), anappropriate acid content is at least 4%, preferably at least 6%, morepreferably at least 8%, and most preferably at least 10% by weight, butnot more than 30%, preferably not more than 20%, more preferably notmore than 18%, and most preferably not more than 15% by weight. For therandom copolymer (b), an appropriate acid content is at least 4%,preferably at least 6%, and more preferably at least 8% by weight, butnot more than 15%, preferably not more than 12%, and more preferably notmore than 10% by weight. Outside the range, a lower acid content maylower resilience, whereas a higher acid content may lowerprocessability.

[0026] The metal ion-neutralized olefin-unsaturated carboxylic acidbinary random copolymer (a) or metal ion-neutralized olefin-unsaturatedcarboxylic acid-unsaturated carboxylate ternary random copolymer (b), tobe commonly referred to as “neutralized random copolymer” hereinafter,may be prepared by partially neutralizing acid groups in theabove-mentioned random copolymer with metal ions.

[0027] Examples of the metal ions for neutralizing acid groups includeNa⁺, K⁺, Li⁺, Zn²⁺, Cu²⁺, Mg²⁺, Ca²⁺, Co²⁺, Ni²⁺ and Pb²⁺. The use ofions such as Na⁺, Li⁺, Zn²⁺ and Mg²⁺ is preferred. Zn2+ is especiallypreferred.

[0028] Such neutralized random copolymers are prepared by neutralizingthe above-mentioned random copolymer with the foregoing metal ions. Forexample, the random copolymers can be neutralized using formates,acetates, nitrates, carbonates, hydrogencarbonates, oxides, hydroxidesor alkoxides of the metal ions. The degree of random copolymerneutralization with the metal ions is not critical.

[0029] Of the neutralized random copolymers, a zinc ion-neutralizedionomer resin is preferred because it allows the material to beincreased in melt flow rate to an appropriate level to mold thematerial.

[0030] The base resin consisting of components (a) and (b) may beobtained using commercially available resins. For example, the randomcopolymer (a) is commercially available under the trade name of Nucrel1560, 1214 and 1035 from DuPont-Mitsui Polychemicals Co., Ltd. and ESCOR5200, 5100 and 5000 from EXXONMOBIL Chemical. The random copolymer (b)is commercially available under the trade name of Nucrel AN4311 andAN4318 from DuPont-Mitsui Polychemicals Co., Ltd. and ESCOR ATX325,ATX320 and ATX310 from EXXONMOBIL Chemical.

[0031] Also the neutralized random copolymer (a) is commerciallyavailable under the trade name of Himilan 1554, 1557, 1601, 1605, 1706and AM7311 from DuPont-Mitsui Polychemicals Co., Ltd., Surlyn 7930 fromE. I. Dupont, and Iotek 3110 and 4200 from EXXONMOBIL Chemical. Theneutralized random copolymer (b) is commercially available under thetrade name of Himilan 1855, 1856, and AM7316 from DuPont-MitsuiPolychemicals Co., Ltd., Surlyn 6320, 8320, 9320 and 8120 from E. I.Dupont, and Iotek 7510 and 7520 from EXXONMOBIL Chemical.Zinc-neutralized ionomer resins such as Himilan 1706, 1557 and AM7316are especially preferred among the neutralized random copolymers.

[0032] The base resin is prepared by blending components (a) and (b) ina weight ratio between 100:0 and 25:75, preferably 100:0 and 50:50, morepreferably 100:0 and 75:25, and most preferably 100:0. With too low aproportion of component (a), a molded part of the material has poorrebound.

[0033] The base resin consisting of components (a) and (b) can also betailored for effective molding by adjusting the blend ratio of therandom copolymer and the neutralized random copolymer as well as theabove-adjusted proportion of components (a) and (b). It is recommendedthat the random copolymer and the neutralized random copolymer beblended in a weight ratio between 0:100 and 60:40, preferably 0:100 and40:60, more preferably 0:100 and 20:80, and most preferably 0:100. Withtoo high a proportion of the random copolymer, the material may becomedifficult to mix and mold.

[0034] Component (e) is an optional component for further improving thefeel and rebound of the ball when hit. In the specification, theabove-described base resin in optional admixture with component (e) isgenerally referred to as “resinous component.” Component (e) is athermoplastic elastomer other than ionomer resins, that is, anon-ionomer thermoplastic elastomer. Illustrative examples of thenon-ionomer thermoplastic elastomer include olefin elastomers, styreneelastomers, polyester elastomers, urethane elastomers, and polyamideelastomers. Of these, olefin elastomers and polyester elastomers arepreferred because a further enhancement of rebound is expectable.

[0035] Commercial products may be used as component (e). For example,the olefin elastomer is commercially available under the trade name ofDynalon from JSR Corp. and the polyester elastomer is commerciallyavailable under the trade name of Hytrel from Dupont-Toray Co., Ltd.

[0036] The amount of component (e) blended is at least 0 part,preferably at least 1 part, more preferably at least 2 parts, even morepreferably at least 3 parts, and most preferably at least 4 parts byweight, per 100 parts by weight of the base resin, while the upper limitis up to 100 parts, preferably up to 60 parts, more preferably up to 40parts, even more preferably up to 20 parts by weight, per 100 parts byweight of the base resin. Too high a proportion of component (e) cancompromise the compatibility of the mixture, resulting in a golf ballwith a substantial decline of durability.

[0037] In the inventive mixture, component (c) is a fatty acid or fattyacid derivative having a molecular weight of 280 to 1,500 whose purposeis to enhance the flow characteristics of the mixture. It has amolecular weight which is much smaller than that of the base resin, andserves to increase the melt viscosity of the mixture. Also, because thefatty acid or fatty acid derivative has a high content of acid groups orderivative moieties thereof, its addition to the material precludes asubstantial loss of rebound.

[0038] The molecular weight of fatty acid or fatty acid derivative (c)is at least 280, preferably at least 300, more preferably at least 330,and most preferably at least 360 and up to 1,500, preferably up to1,000, more preferably up to 600, and most preferably up to 500. Too lowa molecular weight fails to improve heat resistance whereas too high amolecular weight fails to improve flow.

[0039] The fatty acid or fatty acid derivative (c) may be an unsaturatedfatty acid or derivative thereof having a double bond or triple bond inthe alkyl group, or it may be a saturated fatty acid or derivativethereof in which all the bonds on the alkyl group are single bonds. Itis recommended that the number of carbon atoms on the molecule generallybe at least 18, preferably at least 20, more preferably at least 22, andeven more preferably at least 24, but up to 80, preferably up to 60,more preferably up to 40, and even more preferably up to 30. Too fewcarbons may make it impossible to achieve the improved heat resistance,and may also set the acid group content so high as to cause the acidgroups to interact with acid groups present on the base resin,diminishing the flow-improving effects. On the other hand, too manycarbons increases the molecular weight, which may also lower theflow-improving effects.

[0040] Examples of fatty acids (c) include stearic acid,12-hydroxystearic acid, behenic acid, oleic acid, linoleic acid,linolenic acid, arachidic acid and lignoceric acid. Of these, stearicacid, arachidic acid, behenic acid and lignoceric acid are preferred,with behenic acid being most preferred.

[0041] Fatty acid derivatives which may be used as component (c) includemetallic soaps in which the proton on the acid group of the fatty acidhas been substituted with a metal ion. Metal ions that may be used insuch metallic soaps include Na⁺, Li⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Al³⁺,Ni²⁺, Fe²⁺, Fe³⁺, Cu²⁺, Sn²⁺, Pb²⁺ and Co²⁺. Of these, Ca²⁺, Mg2+ andZn²⁺ are especially preferred.

[0042] Examples of the fatty acid derivatives (c) include magnesiumstearate, calcium stearate, zinc stearate, magnesium 12-hydroxystearate,calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesiumarachidate, calcium arachidate, zinc arachidate, magnesium behenate,calcium behenate, zinc behenate, magnesium lignocerate, calciumlignocerate and zinc lignocerate. Of these, magnesium stearate, calciumstearate, zinc stearate, magnesium arachidate, calcium arachidate, zincarachidate, magnesium behenate, calcium behenate, zinc behenate,magnesium lignocerate, calcium lignocerate and zinc lignocerate arepreferred.

[0043] In the practice of the invention, use may also be made of knownmetallic soap-modified ionomer resins, including those described in U.S.Pat. Nos. 5,312,857, 5,306,760 and WO 98/46671, as a combination of thebase resin (consisting of components (a) and (b)) with component (c).

[0044] The golf ball material of the invention includes as essentialcomponent (d) a basic inorganic metal compound capable of neutralizingthe acid groups in the base resin and component (c). As already noted inthe preamble, heating and mixing only a metal soap-modified ionomerresin free of component (d) (e.g., only a metallic soap-modified ionomerresin of the type described in the above-cited patents) results information of a large amount of fatty acid due to an exchange reactionbetween the metallic soap and unneutralized acid groups on the ionomerresin, as shown below. Because the fatty acid thus formed is thermalunstable and readily vaporizes during molding, this causes moldingdefects. In addition, the fatty acid thus formed settles on the surfaceof the molded part, substantially lowering the ability of a paint filmto adhere thereto.

[0045] Here, (1) is an unneutralized acid group present on the ionomerresin, (2) is a metallic soap, (3) is a fatty acid, and X is a metalatom.

[0046] In order to resolve such problems, the present inventionincorporates as component (d) a basic inorganic metal compound whichneutralizes the acid groups present in the base resin and in component(c) for improving the rebound properties of a molded part.

[0047] Incorporating essential component (d) serves to neutralize theacid groups in the base resin and in component (c) to an appropriateextent. These components, when blended together in an optimumproportion, act synergistically to increase the thermal stability of themixture, impart good moldability and enhance rebound characteristics.

[0048] It is recommended that the basic inorganic metal compound (d) behighly reactive with the base resin to form reaction by-products whichare free of organic acid so that the degree of neutralization of themixture may be increased without detracting from thermal stability.

[0049] Exemplary metal ions that can be used in the basic inorganicmetal compound (d) include Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, Zn 2+, Al³⁺, Ni²⁺,Fe²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Sn²⁺, Pb²⁺ and Co²⁺. Examples of the basicinorganic metal compound include well-known basic inorganic fillerscontaining these metal ions, such as magnesium oxide, magnesiumhydroxide, magnesium carbonate, zinc oxide, sodium hydroxide, sodiumcarbonate, calcium oxide, calcium hydroxide, lithium hydroxide andlithium carbonate. Of these, hydroxides and monoxides are preferred.Inter alia, calcium hydroxide and magnesium oxide, especially calciumhydroxide, are preferred since they are more reactive with the baseresin.

[0050] The inventive golf ball material comprising, as described above,a resinous component comprising a base resin consisting of a specificproportion of components (a) and (b), blended with optional component(e), in admixture with specific proportions of component (c) andcomponent (d) has improved thermal stability, flow and moldability, andendows a molded part with outstanding rebound characteristics.

[0051] It is critical that the components (c) and (d) be compounded inrelative proportions per 100 parts by weight of the resinous componentconsisting of components (a), (b) and (e); at least 5 parts, preferablyat least 10 parts, more preferably at least 15 parts, and mostpreferably at least 18 parts by weight, but not more than 80 parts,preferably not more than 40 parts, more preferably not more than 25parts by weight, and most preferably not more than 22 parts by weight,of component (c); and at least 0.1 part, preferably at least 0.5 part,more preferably at least 1 part, and most preferably at least 2 parts byweight, but not more than 10 parts, preferably not more than 8 parts,more preferably not more than 6 parts, and most preferably not more than5 parts by weight, of component (d). Too little component (c) lowers themelt viscosity, resulting in inferior processability, whereas too muchdetracts from the durability. Too little component (d) fails to improvethermal stability and rebound, whereas too much component (d) insteadlowers the heat resistance of the material due to the excess of basicinorganic metal compound.

[0052] While the golf ball material of the invention is arrived at bymixing the resinous component with components (c) and (d), it isrecommended that at least 50 mol %, preferably at least 60 mol %, morepreferably at least 70 mol %, and most preferably at least 80 mol %, ofthe acid groups in the mixture be neutralized. Such a high degree ofneutralization makes it possible to more reliably suppress the exchangereaction which becomes a problem when only the above-described baseresin and the fatty acid or fatty acid derivative are used as in theprior art, and thus prevents the formation of fatty acid. As a result,there can be obtained a material having greatly increased thermalstability, good moldability and a much larger resilience than prior-artionomer resins.

[0053] It is noted that the degree of neutralization refers to thedegree of neutralization of acid groups in the mixture of the base resinand the fatty acid or derivative thereof (c) rather than the degree ofneutralization of an ionomer resin itself which is used as theneutralized random copolymer in the base resin. When the inventivemixture is compared with an ionomer resin alone having an identicaldegree of neutralization, the mixture contains much more metal ions.Then the mixture, when molded, arrives at a higher density of ioniccrosslinks contributing to resilience improvement, with a molded partbeing endowed with greater resilience.

[0054] To more reliably achieve both a high degree of neutralization andsmooth flow, it is recommended that the acid groups in the mixture beneutralized with transition metal ions and alkali metal and/or alkalineearth metal ions. Although transition metal ions have weaker ioniccohesion than alkali metal and alkaline earth metal ions, the combineduse of metal ions of different species to neutralize the acid groups inthe mixture can provide a substantial improvement in flow.

[0055] It is recommended that the molar ratio between the transitionmetal ions and the alkali metal and/or alkaline earth metal ions fall inthe range of from 10:90 to 90:10, preferably from 20:80 to 80:20, morepreferably from 30:70 to 70:30, and most preferably from 40:60 to 60:40.Too low a molar ratio of transition metal ions may fail to providesufficient improvement in flow, whereas too high a molar ratio may lowerresilience.

[0056] Illustrative, non-limiting examples of the metal ions includezinc ions as the transition metal ions, and at least one type of ionselected from among sodium ions, lithium ions and magnesium ions as thealkali metal or alkaline earth metal ions.

[0057] Any known method may be used in obtaining a mixture in which thedesired proportion of the acid groups have been neutralized withtransition metal ions and alkali metal or alkaline earth metal ions. Forexample, specific methods of neutralization with transition metal ions,and in particular zinc ions, include the use of zinc soap as the fattyacid derivative, the inclusion of a zinc-neutralized random copolymer(e.g., zinc-neutralized ionomer resin) as components (a) and (b) in thebase resin, and the use of a zinc compound, typically zinc oxide, as thebasic inorganic metal compound (d).

[0058] The golf ball material of the invention can be prepared for aparticular application by incorporating in the above-described mixtureof essential components whatever additives may be required. For example,where the material is to be used as a cover stock, the mixture may haveadded thereto such additives as pigments, dispersants, antioxidants,ultraviolet absorbers and light stabilizers. Where such additives arecompounded, the addition amount is preferably at least 0.1 part, morepreferably at least 0.5 part, and even more preferably at least 1 partby weight and up to 10 parts, more preferably up to 6 parts, and evenmore preferably up to 4 parts by weight, per 100 parts by weight of theessential components (resinous component+(c)+(d)) combined.

[0059] The golf ball material of the invention can be arrived at byfurnishing a mixture of the above-described essential components andoptional components. For instance, necessary ingredients are heated andmixed at a heating temperature of 150 to 250° C. and in an internalmixer such as a kneading-type twin-screw extruder, a Banbury mixer or akneader. Any desired method may be used to incorporate various additivestogether with the essential components in the golf ball material of theinvention. For example, the additives may be blended with the essentialcomponents, and heating and mixing of all the ingredients carried out atthe same time. Alternatively, the essential components may be pre-heatedand pre-mixed, following which the optional additives may be added andthe overall composition subjected to additional heating and mixing.

[0060] The golf ball material of the invention is preferably adjusted toan appropriate melt flow rate to provide an adequate flow for injectionmolding, that is, to improve moldability. It is recommended that themelt flow rate (MFR) of the material, as measured in accordance withJIS-K7210 at a temperature of 190° C. and under a load of 21.18 N (2.16kgf), be at least 0.5 dg/min, preferably at least 1 dg/min, morepreferably at least 1.5 dg/min, and most preferably at least 2.0 dg/minand not more than 20 dg/min, preferably not more than 10 dg/min, morepreferably not more than 5 dg/min and most preferably not more than 3dg/min. If the mixture has too low or too high a melt flow rate, theprocessability may decrease markedly.

[0061] The golf ball material of the invention is preferably optimizedin the relative absorbance in infrared absorption spectroscopy,representing the ratio of absorbance at the absorption peak attributableto carboxylate anion stretching vibrations normally detected at 1530 to1630 cm⁻¹ to the absorbance at the absorption peak attributable tocarbonyl stretching vibrations normally detected at 1690 to 1710 cm⁻¹.For the sake of clarity, this ratio may be expressed as: (absorbance ofabsorption peak for carboxylate stretching vibrations)/(absorbance ofabsorption peak for carbonyl stretching vibrations).

[0062] Here, “carboxylate stretching vibrations” refers to vibrations bycarboxyl groups from which the proton has dissociated (metalion-neutralized carboxyl groups), whereas “carbonyl stretchingvibrations” refers to vibrations by undissociated carboxyl groups. Theratio in these respective peak intensities depends on the degree ofneutralization. For commonly used ionomer resins having a degree ofneutralization of about 50 mol %, the ratio between these peakabsorbances is about 1:1.

[0063] To improve the thermal stability, flow, moldability and reboundof the golf ball material, it is recommended that the material have acarboxylate stretching vibration peak absorbance which is at least 1.3times, preferably at least 1.5 times, and more preferably at least 2times, the carbonyl stretching vibration peak absorbance. The absence ofa carbonyl stretching vibration peak altogether is especially preferred.

[0064] The thermal stability of the inventive golf ball material can bemeasured by thermogravimetry. It is recommended that, inthermogravimetric analysis, the mixture have a weight loss at 250° C.,based on the weight of the mixture at 25° C., of not more than 2% byweight, preferably not more than 1.5% by weight, and most preferably notmore than 1% by weight.

[0065] It is further recommended that the compounding of the golf ballmaterial be adjusted so as to provide a molded part thereof with a ShoreD hardness of at least 50, preferably at least 53, more preferably atleast 56, even more preferably at least 58, but up to 75, preferably upto 70, more preferably up to 65, even more preferably up to 62. Too higha Shore D hardness may compromise the feel of a golf ball made of thematerial when hit whereas too low a Shore D hardness may lead to adecline of resilience.

[0066] The golf ball material may have any desired specific gravityalthough it is generally advisable for the specific gravity to be atleast 0.9, more preferably at least 0.92, even more preferably at least0.94, but not more than 1.2, more preferably not more than 1.1, evenmore preferably not more than 1.05.

[0067] The golf ball of the invention has a molded part of the golf ballmaterial according to the invention as a constituent component. Thelayer or layers made of the golf ball material may constitute a portionor all of the golf ball. The inventive golf balls may be thread-woundballs, including those in which the cover has a single-layer or amultiple-layer construction, one-piece balls, two-piece balls,three-piece balls, or multi-piece balls having a cover composed of threeor more layers. The type of golf ball is not critical as long as theball has a molded part of the inventive golf ball material as aconstituent component.

[0068] The inventive golf balls may be manufactured by preparing variousmixtures for making one-piece balls, the solid centers of thread-woundgolf balls, the solid cores of solid golf balls, or cover stock (for atleast one layer in cores and covers composed of two or more layers) inaccordance with the above-described golf ball material formulation ofthe invention, then using the mixture in accordance with a golf ballmanufacturing method known to the art.

[0069] When the cover of a golf ball is made of the golf ball materialaccording to the present invention, the core may be either athread-wound core or a solid core and may be produced by a conventionalmethod.

[0070] For example, a solid core may be produced by preparing a rubbercomposition composed of 100 parts by weight of cis-1,4-polybutadiene;from 10 to 60 parts by weight of one or more vulcanizing or crosslinkingagents selected from among α,β-monoethylenically unsaturated carboxylicacids (e.g., acrylic acid, methacrylic acid) or metal ion-neutralizedcompounds thereof and functional monomers (e.g., trimethylolpropanemethacrylate); from 5 to 30 parts by weight of a filler such as zincoxide or barium sulfate; from 0.5 to 5 parts by weight of a peroxidesuch as dicumyl peroxide; and, if necessary, from 0.1 to 1 part byweight of an antioxidant. The resulting rubber composition can be formedinto a solid spherical core by press vulcanization to effectcrosslinkage, followed by compression under heating at 140 to 170° C.for a period of 10 to 40 minutes.

[0071] Production of a thread-wound golf ball core may be carried outusing either a liquid or a solid center. In the case of a liquid center,a hollow spherical center envelope may be formed from theabove-described rubber composition, for example, and a liquid filledinto this envelope by a well-known method. If a solid center is usedinstead, the solid center may be produced by the solid core productionmethod described above. Thereafter, rubber thread is wound in astretched state about the center to form the core. Use may be made ofrubber thread produced by a conventional method. For example, rubberthread is prepared by compounding natural rubber or synthetic rubbersuch as polyisoprene with various additives (e.g., antioxidants,vulcanization accelerators and sulfur) to form a rubber composition,which is molded and vulcanized.

[0072] The golf balls using the various types of cores described aboveand falling within the scope of the invention can be produced by formingthe cover from the inventive golf ball material. In one such method, asingle-layer or multi-layer core prefabricated according to the type ofball to be manufactured is placed in a mold, and the inventive materialis heated, mixed and melted, then injection-molded over the core. Inthis case, the golf ball manufacturing operation can be carried outunder conditions which assure that the material maintain excellentthermal stability, flow and moldability. The resulting golf ball has ahigh rebound.

[0073] The method used to produce the cover is not limited to the methoddescribed above. In an alternative method which can be used herein, apair of hemispherical cups is molded from the inventive golf ballmaterial, following which the cups are placed over a core and moldedunder heat (120 to 170° C.) and pressure for 1 to 5 minutes.

[0074] No particular limitation is imposed on the thickness of the covermade of the inventive material, although the cover is generally formedto a thickness of at least 0.5 mm, preferably at least 0.9 mm, morepreferably at least 1.1 mm, but up to 3 mm, preferably up to 2.5 mm,more preferably up to 2.0 mm. The cover in the golf balls of theinvention is not limited to one layer, and may instead have a multilayerconstruction of two or more layers. If the cover has a multilayerconstruction, the golf ball material of the invention may be used eitherat the interior of the multilayer construction or as the outermost layerof the cover. In the case of a single-layer cover (for two-piece golfball), it is highly advantageous for the inventive material to serve asthe cover material.

[0075] If the ball is a multi-piece golf ball having a cover of two ormore layers, the inventive material is most preferably used as a layerof the cover other than the outermost layer—that is, as an inner layerof the cover. In this embodiment, the cover outermost layer ispreferably formed of a polyurethane elastomer because it cooperates withthe cover inner layer so as to impart very high rebound to the golfball.

[0076] The golf ball may have a plurality of dimples formed on itssurface, and the cover may be administered various treatment such assurface preparation, stamping and painting. In particular, a golf ballcover made of the inventive material ensures ease of work involved inadministering such surface treatment. The outermost layer of theinventive material ensures improvements in working including painting.

[0077] The golf ball of the invention may be a golf ball in which theinventive golf ball material is used other than as the cover stockdescribed above. For example, it may be a golf ball arrived at by usingthe inventive material as a one-piece golf ball material or as a corematerial. In this case, production may be carried out using well-knownmaterials and methods.

[0078] In the golf balls manufactured as described above, the diameter,weight, hardness and other parameters of the cover, solid or liquidcenter, solid core or thread-wound core, and one-piece golf balls, whilenot subject to any particular limitations, may be adjusted asappropriate, insofar as the objects of the invention are attainable.

[0079] The golf ball of the invention may be manufactured for use intournaments by giving it a diameter and weight which conform with theRules of Golf. That is, the ball may be produced to a diameter of notless than 42.67 mm and a weight of not greater than 45.93 g.

EXAMPLE

[0080] Examples of the invention and comparative examples are givenbelow by way of illustration, and are not intended to limit theinvention.

Examples 1-8 and Comparative Examples 1-9

[0081] Using a core material composed primarily ofcis-1,4-polybutadiene, a solid core was produced having a diameter of38.6 mm, a weight of 35.1 g, and a deflection of 3.1 mm under a load of980 N (100 kg).

[0082] Cover materials of the compositions shown in Tables 1 and 2 weremixed at 230° C. with a kneading-type twin-screw extruder and preparedin the form of pellets. In each of the examples, the cover material wasinjected into a mold in which the solid core prepared above had beenplaced, giving a two-piece solid golf ball having a diameter of 42.8 mmand a cover thickness of 2.1 mm.

Example 9 and Comparative Examples 10 and 11

[0083] Using a core material composed primarily ofcis-1,4-polybutadiene, a solid core was produced having a diameter of36.4 mm, a weight of 29.4 g, and a deflection of 3.7 mm under a load of980 N (100 kg).

[0084] In Example 9, the cover material described above in Example 1 wasinjection-molded over the core so as to form a cover inner layer havinga thickness of 1.7 mm. Similarly, in Comparative Examples 10 and 11, therespective cover materials described in Comparative Examples 1 and 2were injection-molded over the core so as to form a cover inner layerhaving a thickness of 1.7 mm. Next, in each of the three examples, theouter cover material shown in Table 3 was injection-molded over thecover inner layer, thereby giving a three-piece solid golf ball having adiameter of 42.8 mm.

[0085] The following characteristics were measured or evaluated for thegolf balls obtained in each of the above examples. The results are alsoshown in Tables 1 to 3.

[0086] Ball Hardness:

[0087] Measured as the deflection (in millimeters) of the ball under aload of 980 N (100 kg).

[0088] Initial Velocity:

[0089] Measured using the same type of initial velocity instrument asthat approved by the United States Golf Association (USGA), and inaccordance with USGA rules.

[0090] Relative Absorbance of Carboxylate Absorption Peak:

[0091] A transmission method was used to measure the infrared absorptionof the samples. In the infrared absorption spectrum for a sampleprepared to such a thickness as to make the peak transmittanceassociated with hydrocarbon chains observed near 2900 cm⁻¹ about 90%,the absorption peak due to carbonyl stretching vibrations (1690 to 1710cm⁻¹) was assigned an absorbance value of 1 and the ratio thereto of theabsorption peak due to carboxylate anion strength vibrations (1530 to1630 cm⁻¹) was computed as the relative absorbance.

[0092] Percent Weight Loss:

[0093] Prior to measurement, samples were dried in a dry hopper at 50° Cfor 24 hours for eliminating the influence of moisture.Thermogravimetric analysis was carried out on approximately 5 mg samplesby raising the temperature from 25° C. to 300° C. in a nitrogenatmosphere (flow rate, 100 ml/min) at a rate of 10° C./min, thencalculating the percent loss in the sample weight at 250° C. relative tothe sample weight at 25° C.

[0094] Degree of Neutralization:

[0095] Of all the acid groups (including acid groups on fatty acids orfatty acid derivatives) present in the mixture, the mole fraction ofacid groups neutralized with transition metal ions was computed from theacid content, degree of neutralization, and molecular weight of thestarting materials.

[0096] Compounding Ratio of Transition Metal Ions:

[0097] The mole fraction of transition metal ions among the metal ionswhich neutralize the acid groups present in the mixture was computedfrom the acid content, degree of neutralization and molecular weight ofthe starting materials.

[0098] Melt Flow Rate:

[0099] The melt flow rate of the material was measured in accordancewith JIS-K7210 at a temperature of 190° C. and under a load of 21.18 N(2.16 kgf).

[0100] Extrudability:

[0101] Each of the cover materials was worked at 200° C. in anintermeshing co-rotating type twin-screw extruder (screw diameter, 32mm; main motor output, 7.5 kW) such as is commonly used for mixingmaterials, whereupon it was rated for processability as follows.

[0102] Good: Extrudable

[0103] Poor: Cannot be extruded due to excess loading

[0104] Trade names and materials mentioned in the tables are describedbelow.

[0105] Nucrel 1560: Ethylene-methacrylic acid copolymer made byDuPont-Mitsui Polychemicals Co., Ltd.

[0106] Himilan 1605: Sodium neutralized ionomer resin produced byDuPont-Mitsui Polychemicals Co., Ltd.

[0107] Himilan 1706: Zinc neutralized ionomer resin produced byDuPont-Mitsui Polychemicals Co., Ltd.

[0108] Himilan 1601: Sodium neutralized ionomer resin produced byDuPont-Mitsui Polychemicals Co., Ltd.

[0109] Himilan 1557: Zinc neutralized ionomer resin produced byDuPont-Mitsui Polychemicals Co., Ltd.

[0110] Nucrel AN4318: Ethylene-methacrylic acid-acrylate copolymer madeby DuPont-Mitsui Polychemicals Co., Ltd.

[0111] Behenic acid: Produced by NOF Corporation under the trade nameNAA-222S.

[0112] Calcium hydroxide: Produced by Shiraishi Industry Co., Ltd. underthe trade name CLS-B.

[0113] Dynalon 6100P: Thermoplastic olefin elastomer produced by JSRCorp.

[0114] Dynalon 6200P: Thermoplastic olefin elastomer produced by JSRCorp.

[0115] Hytrel 3046: Thermoplastic polyester elastomer produced byDuPont-Toray Co., Ltd.

[0116] Pandex T7298: Thermoplastic urethane elastomer produced byDainippon Ink & Chemicals, Inc. TABLE 1 Example 1 2 3 4 5 6 7 8Composition (pbw) Component (a) Nucrel 1560 30.0 Himilan 1605 50.0 42.542.5 42.5 42.5 27.5 28.3 14.2 Himilan 1706 50.0 42.5 42.5 42.5 42.5 27.528.3 14.2 Component (b) Nucrel 15.0 15.0 10.0 10.0 15.0 43.4 71.6 AN4318Component (c) Behenic acid 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Calcium20.0 stearate Component (d) Calcium 2.5 2.8 0.5 2.5 2.5 3.5 3.4 3.9hydroxide Dynalon 6100P 5.0 Hytrel 3046 5.0 Titanium 2 2 2 2 2 2 2 2dioxide Cover stock properties Extrudability good good good good goodgood good good Transition 47 42 32 44 44 32 33 19 metal ion compoundingratio (%) Melt flow 2.0 2.0 1.5 2.0 2.0 2.0 1.9 1.8 rate (dg/min) Weightloss 0.7 0.6 1.5 0.6 0.6 0.8 0.6 0.5 (wt %) Relative 1.5 1.5 1.5 1.4 1.41.5 1.7 1.8 absorbance of carboxylate peak Cover hardness 62 60 60 60 6060 57 54 (Shore D) Specific 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.97gravity Ball properties Weight (g) 45.2 45.2 45.2 45.2 45.2 45.2 45.245.2 Hardness (mm) 2.70 2.72 2.72 2.72 2.72 2.72 2.75 2.78 Initial 77.176.9 76.9 76.9 76.9 76.8 76.7 76.5 velocity (m/s)

[0117] TABLE 2 Comparative Example 1 2 3 4 5 6 7 8 9 Composition (ppw)Component (a) Nucrel 1560 Himilan 1605 50 50 50 42.5 42.5 28.3 28.3 14.214.2 Himilan 1706 50 50 50 42.5 42.5 28.3 28.3 14.2 14.2 Component (b)Nucrel AN4318 15 15 43.4 43.4 71.6 71.6 Component (c) Behenic acidCalcium stearate 20 20 20 20 Component (d) Calcium hydroxide 2.5 2.8 3.43.9 Dynalon 6100P Hytrel 3046 Titanium dioxide 2 2 2 2 2 2 2 2 2 Coverstock properties Extrudability good good poor good poor good poor goodpoor Transition metal ion 67 36 47 33 63 27 33 17 20 compounding ratio(%) Melt flow rate (dg/min) 1.9 2.2 — 1.9 — 1.8 — 1.8 — Weight loss (wt%) 0.5 2.8 — 2.8 — 2.8 — 2.8 — Relative absorbance of 0.9 1.4 — 1.3 —1.1 — 1.0 — carboxylate peak Cover hardness (Shore D) 62 63 — 61 — 58 —54 — Specific gravity 0.98 0.97 — 0.97 — 0.97 — 0.97 — Ball propertiesWeight (g) 45.3 45.2 — 45.2 — 45.2 — 45.2 — Hardness (mm) 2.70 2.69 —2.71 — 2.74 — 2.78 — Initial velocity (m/s) 76.8 76.9 — 76.7 — 76.5 —76.3 —

[0118] TABLE 3 Comparative Example Example 9 10 11 Cover inner layerComposition (pbw) Component (a) Himilan 1605 50 50 50 Himilan 1706 50 5050 Component (c) Behenic acid 20 Calcium stearate 20 Component (d)Calcium hydroxide 2.5 Titanium dioxide 2 2 2 Cover outer layerComposition (pbw) Pandex T7298 100 100 100 Titanium dioxide 2 2 2 Coverhardness (Shore D) 45 45 45 Specific gravity 1.19 1.19 1.19 Ballproperties Weight (g) 45.2 45.2 45.2 Hardness (mm) 2.9 2.9 2.89 Initialvelocity (m/s) 77.1 76.9 76.9

[0119] The cover stock of Example 1 had superior heat resistance andresilience to the cover stocks of Comparative Examples 1 to 3 containingthe same base resin and lacking component (c) and/or (d).

[0120] The cover stocks of Examples 2 to 5 had superior heat resistanceand resilience to the cover stocks of Comparative Examples 4 and 5containing the same base resin and lacking component (c) or (d).

[0121] The cover stock of Example 6 had superior heat resistance andresilience to the cover stock of Comparative Example 4.

[0122] The cover stock of Example 7 had superior heat resistance andresilience to the cover stocks of Comparative Examples 6 and 7containing the same base resin and lacking component (c) or (d).

[0123] The cover stock of Example 8 had superior heat resistance andresilience to the cover stocks of Comparative Examples 8 and 9containing the same base resin and lacking component (c) or (d).

[0124] Also, the cover stocks of Comparative Examples 3, 5, 7 and 9 weredifficult to extrusion mold.

[0125] The three-piece solid golf ball of Example 9 using the coverstock of Example 1 as the cover inner layer had superior rebound to thethree-piece solid golf balls of Comparative Examples 10 and 11 using thecover stocks of Comparative Examples 1 and 2 as the cover inner layer

Examples 10-13 and Comparative Examples 12-16

[0126] Using a core material composed primarily ofcis-1,4-polybutadiene, a solid core was produced having a diameter of36.4 mm, a weight of 29.4 g, and a deflection of 3.4 mm under a load of980 N (100 kg).

[0127] An inner cover material of the composition shown in Table 4 wasinjection molded around the solid core to form a cover inner layer of1.7 mm thick. An outer cover material of the composition shown in Table4 was injection molded around the inner layer to form a cover outerlayer, giving a three-piece solid golf ball having a diameter of 42.8mm.

[0128] The golf balls thus obtained were examined for initial velocity,with the results shown in Table 4. TABLE 4 Example Comparative Example10 11 12 13 12 13 14 15 16 Cover inner layer Composition (pbw) Component(a) Himilan 1605 35.0 35.0 45.0 35.0 35.0 45.0 Himilan 1706 35.0 35.045.0 35.0 35.0 45.0 Himilan 1601 40.0 40.0 50.0 Himilan 1557 40.0 40.050.0 Component (e) Dynalon 6200P 30.0 20.0 10.0 30.0 20.0 10.0 Dynalon6100P 30.0 30.0 Component (c) Behenic acid 20.0 20.0 20.0 20.0 Component(d) Calcium hydroxide 2.5 2.3 2.6 2.8 Extrudability good good good goodgood good good good good Melt flow rate (dg/min) 2.0 2.0 2.0 2.0 1.8 1.52.0 1.9 2.1 Cover hardness (Shore D) 56 56 56 60 56 56 56 60 60 Weightloss (wt %) 0.5 0.5 0.5 0.6 0.5 0.5 0.5 0.5 0.5 Specific gravity 0.950.95 0.95 0.96 0.95 0.95 0.95 0.96 0.96 Cover outer layer Composition(pbw) Thermoplastic polyurethane 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 elastomer Titanium dioxide 2.0 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 Cover hardness (Shore D) 50 50 50 50 50 50 50 50 50 Specificgravity 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 Ball propertiesWeight (g) 45.2 45.2 45.2 45.3 45.2 45.2 45.2 45.3 45.3 Hardness (mm)2.76 2.72 2.75 2.61 2.72 2.72 2.72 2.56 2.58 Initial velocity (m/s) 77.277.3 77.1 77.3 76.8 76.8 76.6 77.0 76.8

[0129] The golf ball material of the invention has good thermalstability, flow characteristics and moldability, and can be molded intoa part exhibiting excellent rebound, ensuring the manufacture of golfballs with high performance. The golf balls of the invention having amolded part of the inventive golf ball material as a constituentcomponent can be manufactured easily and efficiently, and have excellentrebound.

[0130] Japanese Patent Application Nos. 2000-355717 and 2001-178393 areincorporated herein by reference.

[0131] Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A golf ball material comprising a mixture which is composed of: 100parts by weight of a resinous component consisting essentially of a baseresin having (a) an olefin-unsaturated carboxylic acid binary randomcopolymer or a metal ion-neutralized olefin-unsaturated carboxylic acidbinary random copolymer or both, blended with (b) an olefin-unsaturatedcarboxylic acid-unsaturated carboxylate ternary random copolymer or ametal ion-neutralized olefin-unsaturated carboxylic acid-unsaturatedcarboxylate ternary random copolymer or both, in a weight ratio of 100:0to 25:75, and (e) a non-ionomer thermoplastic elastomer, said base resinand said elastomer being blended in a weight ratio of 100:0 to 50:50;(c) 5 to 80 parts by weight of a fatty acid or fatty acid derivative orboth, having a molecular weight of 280 to 1,500; and (d) 0.1 to 10 partsby weight of a basic inorganic metal compound capable of neutralizingacidic groups left unneutralized in the base resin and component (c). 2.The golf ball material of claim 1, wherein the mixture has a melt flowrate of 0.5 to 20 dg/min.
 3. The golf ball material of claim 1, whereinat least 50 mol % of the acid groups in the mixture are neutralized withmetal ions.
 4. The golf ball material of claim 1, wherein the metal ionsare comprised of at least one type of transition metal ion and at leastone type of alkali metal or alkaline earth metal ion.
 5. The golf ballmaterial of claim 4, wherein the transition metal ions and the alkalimetal or alkaline earth metal ions are in a molar ratio of 10:90 to90:10.
 6. The golf ball material of claim 1, wherein the metalion-neutralized random copolymer in said base resin includes a zincion-neutralized ionomer resin.
 7. The golf ball material of claim 1,wherein the total content of random copolymers and the total content ofmetal ion-neutralized random copolymers in said base resin are in aweight ratio of 0:100 to 60:40.
 8. The golf ball material of claim 1,wherein component (c) is at least one member selected from the groupconsisting of stearic acid, behenic acid, arachidic acid, lignocericacid and derivatives thereof.
 9. The golf ball material of claim 1,wherein component (d) is calcium hydroxide.
 10. The golf ball materialof claim 1, wherein component (e) is at least one member selected fromthe group consisting of an olefin elastomer, styrene elastomer,polyester elastomer, urethane elastomer, and polyamide elastomer.
 11. Agolf ball comprising a molded part of the golf ball material accordingto any one of claims 1 to
 10. 12. The golf ball of claim 11, wherein themolded part has a Shore D hardness of 50 to
 75. 13. The golf ball ofclaim 11 which is a multi-piece solid golf ball comprising a core, acover inner layer and a cover outer layer, wherein the cover inner layeris a molded part of the golf ball material according to any one ofclaims 1 to 10.